Polyesters containing tertiary nitrogen atoms

ABSTRACT

The invention relates to novel linear polyesters containing hydroxy end groups and an N,N-bis-( Beta -sec.hydroxy-alkyl)-palkylphenylamine and certain dicarboxylic acids condensed therein. These novel polyesters are useful as accelerators for mixtures of unsaturated polyesters and copolymerizable monomers which harden at room temperature after the addition of a diacyl peroxide catalyst.

United States Patent Eimers et al.

.1451 Sept. 11, 1973 POLYESTERS CONTAINING TERTIARY NITROGEN ATOMSInventors: Erich Eimers, Krefeld; Hans Rudolph; Werner Kloker, both ofKrefeld-Bockum, all of Germany Bayer Aktiengesellschaft, Leverkusen,Germany Filed: Oct. 28, 1971 Appl. No.: 193,553

Related U.S. Application Data Division of Ser. No. 64,822, Aug. 18,1970, Pat. No. 3,646,160.

Assignee:

Foreign Application Priority Data Aug. 29, 1969 Germany P 19 43 954.4

U.S. Cl. 260/485 G, 260/468 K C07c 69/44 Field of Search 260/475 P, 485G References Cited OTHER PUBLICATIONS Sulzberg et al., Macromolecules1969, 2(2) pp. 146-153, Man-April (1969).

Primary Examiner-Lorraine A. Weinberger piary?! mm e r i-mhw Skell Y W Attorney- Arthur G. Connolly, Nicholas E. Oglesby, Jr. et al.

2 Claims, No Drawings 1 2 POLYESTERS CONTAINING TERTIARY impart a highreactivity to the polyester compositions NITROGEN ATOMS after additionof a diacyl peroxide, which remains largely constant even afterprolonged storage of the CROSS'REFERENCE To RELATED APPuCATlON mixturesprior to the addition of the peroxide, but

This application is a division of application Ser. No. 5 above all thatthe cured products hardly discolour, in 64,822 filed Aug. 18, 1970 andnow U.S. Pat. No. particular even on ageing.

,l The new polyesters can be manufactured by polyconhe inventionPrOvldeS polyesters contamms ternary densation of suitable dicarboxylicacids of the formula nitrogen atoms, of formula 2 RN ""6" o it B I F 5'l I[O -CII2N-CHzOOCRaCO -CHrN-CH;(|3OH it H H H I R: i n

wherein '7 i i v i i (I) q R denotes the methyl or ethyl group,H0-dRab-OH R denotes an alkyl group with one to six carbon 7 atoms, witha greater or lesser molar excess of a tertiary amine R denotes asaturated, straight-chain or branched, of formula alkylene group withfour to 12 carbon atoms, or a saturated cycloalkylene group or anarylene group of which the dicarboxylic acids do not form cyclican'hydrides, and n denotes an integer from 2 to 100. The inventionfurther provides a curable resin composition comprising an unsaturatedpolyester dissolved in a monomer copolymerizable therewith and 0.1 to 5R1 per cent by weight of a polyester of the invention as a curingaccelerator. These compositions are curable without heat applying by thefurther addition of a diacyl peroxide.

It is known from the U.S. Pat. No. 2,812,313 to react tertiary amines offormula with heating, optionally with the addition of esterificationcatalysts and with inert gas being passed through.

As greater said excess of the tertiary amine is as lower is the value ofn in formula 1 and vice versa. Suitable excesses are, for example, from100 to about 1 and preferable from about 50 to about 10 mol percent.

Amines which correspond to the above formula are, for example,N-bis-(B-hydroxypropyl)-p-toluidine, N-bis-(,B-hydroxypropyl)-p-tert.butylaniline and N-bis-(fi-hydroxybutyl)-p-ethylaniline.

Suitable dicarboxylic acids are, for example, adipic acid, pimelic acid,sebacic acid, cyclohexane-l,4- dicarboxylic acid,cyclohexane-l,Z-trans-dicarboxylic acid, isophthalic acid andterephthalic acid.

The Table which follows indicates the effect of adding variousnitrogen-containing polyesters (1,2,3 and 4) to two different polyestercasting resins after adding 3 percent by weight of benzoyl peroxide pastin each case. Accelerator 1 denotes the known polycondensation productfrom 0,78 mol equivalent of phthalic anhydride and 1 mol equivalent ofN-bis-(B-hydroxyethyl)-p-toluidine, and accelerator 3 denotes thepolywherein R denotes a phenylene radical which is optionallyalkyl-substituted, preferably methyl-substituted, in the p-position, Zoptionally denotes a hydroxyl group and x denotes an integer from i to6, preferably 2, with a dicarboxylic acid and preferably phthalicanhydride to give a polyester, and also to add this as a cureaccelerator to unsaturated polyester resin compositions. The polyestersof the present invention differ from these polyesters, obtainableaccording to said Patent, in four respects: The end groups must behydroxyl groups, the alkyl groups on the nitrogen carry a secondaryhydroxyl group in the fl-position to the amino group, the substituentsof the phenylene radicals locfndelisation p' f fiom i q i lent ofadicated in the p-position to the nitrogen atom are re- P acid and againmol equivalent of '(fistricted to loweralkyl radicals, and thedicarboxylic y y y P and accelerator denotes acids used for themanufacture of the polyesters are rethe P P of 1 mol equwalent strictedto those in which the radical linking the two adipic add and again 1equivalent of -(B' carboxyl groups to one another corresponds tothe'rady y y )-P- These accelerators do not ical R of the above formula,with straight-chain or correspond to the invention; only accelerator 4correbranched alkylene groups with four to 12 carbon atoms SPOIIdS theinvention; it is the eotldensation Product being preferred. from 0.78mol equivalent of adlplc acid and 1 mol The new polyesters have theadvantage compared equivalent of N-bis-(B-hydroxypropyl)-p-toluidine.with those known from the Patent mentioned above Each of thesepolyesters has an acid number of about that when added as curingaccelerators to unsaturated I0, is stabilised by adding 0.1 per cent byweight of hypolyester resin mixtures as described in said patent theydroquinone, and is dissolved in styrene at to C to give a solution of 70percent by weight solids content.

The polyester casting resin A is a 69 per cent by weight solution of apolyester of acid number 32 from 542] parts by weight of phthalicanhydride, 3210 parts by weight of maleic anhydride and 5616 parts byweight of 1,2-propylene glycol, in styrene, having a viscosity of 300 c?at 20C, and stabilised by adding 0.009 per cent by weight oftoluhydroquinone and 20 ppm of After weathering the curing products inthe Weatherometer, the samples with accelerators l and 2 were lightbrown after 100 hours and red-brown after 250 hours, whilst the sampleswith accelerator 4 barely showed a yellowish discolouration after 100hours and only a weak yellowish discolouration after 250 hours.

What is claimed is:

1. Polyesters of the formula:

R Ilt F ([2 R R I i I 1 HO? ---CHgI !I-CHq( J-O-C-R1( -O C CH ITICH;C--OII ll 11 1'! i i Amount Colour of 70% index of strength Percent thecured styrene N in the Immediate After 1 week After 2 weeks After 4weeks moulding solution casting (iodine added, resin Gel Curing GelCuring Gel Curing Gel Curing colour percent solution time time time timetime time time time index) Casting resin A Accelerator:

1 2. 5 0. 0812 4. 5 8. 75' 5. 5' 6. 5' 6. 5 11. 25 6. 5' 11. 25130-160 1. 2 0. 0419 6. 25' 12' 11 18' 12 16. 5 12 16. 60-80 6. 0 0. 1609. 25 18' Not measured 9.5 18.5 1. 2 0. 0386 5.25 10. 6' 11.75 6. 7512.75 7' 12. 75 60-80 Casting resin B 2. 5 0.0812 5. 25 Not measured 8.6 13. 0' 130-160 1. 5 0.0525 7. 0' 6' 8.5 9. 75' 15. 3' 10. 16. 0'80-130 1. 5 0 0483 5. 5 10.0 5. 5 10.75 6. 0' 11. 0' 6. 0 11. 0 60-80 1Approximately 100.

copper naphthenate. wherein R is methyl or ethyl, R, is alkyl havingfrom The polyester casting resin B is a 65 percent by weight solution ofa polyester of acid number 23 from 3292 parts by weight of phthalicanhydride, 3270 parts by weight of maleic anhydride and 4438 parts byweight of 1,2-propylene glycol in styrene, having a viscosity of 1100 c?at 20C, stabilised by the addition of 0.025 per cent by weight ofhydroquinone.

one to six carbon atoms, R; is alkylene having from four to 12 carbonatoms or cyclohexylene of which the dicarboxylic acids do not formcyclic anhydrides and n is an integer of from 1 to 100.

2. The polyester of claim 1 wherein R and R are each methyl and R is(CH,),.

i t k

2. The polyester of claim 1 wherein R1 and R2 are each methyl and R3 is-(CH2)4-.